Dialkylphenyl-n-methyl-haloacetyl carbamates

ABSTRACT

COMPOUNDS HAVING THE GENERAL FORMULA   1-(CL-CH2-CO-N(-CH3)-COO-),3-(CH3-),R&#39;&#39;-BENZENE   WHEREIN R&#39;&#39; REPRESENTS THE METHYL GROUP ATTACHED TO THE 4- OR 5-POSITION OF THE BENZENE RING OR THE ISOPROPYL GROUP ATTACHED TO THE 5-POSITION OF THE BENZENE RING, POSSESS GOOD INSECTICIDAL PROPERTIES WITH LOW TOXICITY TO HOMOTHERMAL ANIMALS.

"United States Patent 3,790,621 DIALKYLPHENYL-N-METHYL-HALOACETYL CARBAMATES Miehihiko Sakai and Yasuo Sato, Kyoto, and Rokuya Morimoto, Kazuo Konishi, and Katsuyuki Maki, Osaka, Japan, assignors to Takeda Chemical Industries, Ltd., Osaka, Japan No Drawing. Filed May 12, 1969, Ser. No. 823,968 Claims priority, applticatioiasJgpan, May 11, 1968,

Int. c1. (30% 125/06 US. Cl. 260-479 C 4 Claims ABSTRACT OF THE DISCLOSURE Compounds having the general formula R CH:

COCHiCl Ha wherein R represents the methyl group attached to the 4- or S-position of the benzene ring or the isopropyl group attached to the 5-position of the benzene ring, possess good insecticidal properties with low toxicity to homothermal animals.

This invention is concerned with an insecticidal composition.

I-Ieretofore, it has been known that although substituted phenyl N-methyl carbamate derivatives represented by the formula (R ll @ooounom (wherein R is a substituent and n is an integer) possess insecticidal properties, they are accompanied by such a serious defect as being highly toxic to homothermal animals.

For the purpose of eliminating the above defect, it has been proposed to replace the hydrogen atom of the carbamic acid compound (I) with an acetyl group to produce compounds of the Formula II:

"ice

mates with a chloroacetyl group, that is, the compounds of the formula (methyl or isopropyl) 000mm (III) exhibit a possibility of suiting the afore-mentioned purpose.

We have continued an extensive work to reach a further finding that, in these compounds represented by the Formula III, toxicity to homothermal animals and residual pesticidal properties are greatly influenced by the number of the substituents on the benzene ring, namely, the compounds of the Formula 111 in which the number of the substituents on the benzene ring is 1 or not less than 3 unexpectedly show substantially no pesticidal activity, and that even if two substituents are substituted on the benzene ring, the pesticidal activity is also influenced by the position of the substituents, namely, among the compounds of the Formula III in which two substituents are substituted on the benzene ring, only the 3,5-dimethyl-, 3,4-dimethyland 3-methy1-S-isopropylphenyl N-methyl N-chloroacetyl carbamates show effective residual insec ticidal activity as well as low toxicity to homothermal animals.

This invention is the culmination of the above findings.

It is an object of the present invention to provide new chloroacetyl carbamates which show efiective residual insecticidal activity and low toxicity to homothermal animals.

Another object is to provide an insecticidal composition having etfective residual insecticidal activity and low toxicity to homothermal animals.

Other objects and advantages of this invention will further become apparent hereinafter.

The chloroacetyl carbamates of the present invention are represented by the general formula COCHaCl Chlororaeet l halide Q-ooomacm y CH;

R CH;

0 C O N\ GOCHaCl CH:

The reaction may be eifected at room temperature and can be accelerated by heating, if desired.

The chloroacetyl halide, which is exemplified by chloroacetyl chloride and chloroacetyl bromide, is generally used in an amount of about 2 to 3 moles relative to one mole of the starting material. The reaction may be conducted in the presence or absence of a solvent such as benzene, toluene and xylene.

Insecticidal compositions of the present invention may be prepared, for example, by dissolving or dispersing one or more of 3,4-dimethyl-, 3,5-dimethyland 3-methyl-5- isopropylphenyl N-methyl N-chloroacetyl carbamates in a suitable liquid carrier, or, alternatively, admixing them with a suitable solid carrier, or allowing them to be adsorbed on the solid carrier.

If required, the compositions may further be admixed with emulsifiers, dispersing agents, suspension aids, extenders, penetrating agents, wetting agents, thickeners, stabilizers, etc., which may generally be usable for compounding agricultural formulations, to prepare oily preparations, emulsions, wettable powders, dry powders, pellets, tablets, sprays and the like.

Generally speaking, the suitable concentration of the eifective constituents ranges from to 90% in the case of emulsion and other liquid preparations, and from 0.1

to 10% for oily preparations, wettable powders, etc., although the said ranges may be modified as desired depending on any particular application form.

It should be understood that emulsions, wettable powders and the like may be diluted with Water, for instance, to 500-2000 times as much as the initial volume.

The liquid carriers which may be conveniently employed 'for the compositions of the present invention include, for example, water, alcohols (cg. methyl alcohol, ethyl alcohol, ethylene glycol, etc.), ketones (e.g. acetone, methyl-ethyl ketones, etc.), ethers (e.g. dioxane, tetrahydrofuran, Cellosolve, etc.) aliphatic hydrocarbons (e.g. gasoline, kerosene, machine oil, fuel oil, etc.), aromatic hydrocarbons (e.g. benzene, toluene, xylene, solvent naphtha, methylnaphthalene, etc.), organic bases (e.g. pyridine, collidine, etc.), and amides (e.g. dimethylformamide etc.), esters (cg. ethyl acetate etc.), nitriles (e.g. acetonitrile etc.), and the like.

Such carriers may be employed either singly or in combination.

As the said solid carrier, vegetable powders (eg. soybean powder, tabacco powder, Walnut powder, flour charcoal powder, etc.), mineral powder (e.g. clays: such as kaolin, bentonite, acid clay, etc., tales such as talc, soap stone, etc., and silica such as diatomaceous earth, mica powder, etc.), as well as alumina, silica gel, sulfur powder, activated carbon, etc., may be successfully employed either or in various combinations.

The surface active agents to be employed as the extender, emulsifier, penetrating agent, dispersing agent, solubilizing agent, etc. mentioned hereinbefore may be exemplified by soaps, sulfuric acid esters of high alcohols, olefine sulfate, sulfonated oils, ethanolamine, higher fatty acid esters, alkylarylsulfonates, quaternary ammonium salts, alkyleneoxide type surfactants, and the like.

In addition to those agents mentioned above, it is also possible, for the purpose stated in the foregoing to employ, if required, such substances as casein, gelatin, agar, starch, bentonite, aluminum hydroxide, etc.

To these preparations may be further added various insecticides, nematocides, fungicides, herbicides, plant growth regulators, synergists, inducing agent, repellents, attractants, etc., which if required, may be blended with various nutrients, fertilizers, and the like so far as they do not adversely effect the purpose of this invention.

The present compositions are observed to have the effect to kill a wide variety of insects, and exterminate those harmful animals as exemplified below or at least lessen remarkably the number of surviving animals: The examples of plant feeding insects, etc., are

Field cricket, Acheta assimilis German cockroach, Blattelld g'e rmanica American cockroach, Periplaneta america'nc Oriental cockroach, Blatta orientalis.

Desert locust, Locust migratorz'a Gladiolus thrips, T aenz'othrips simplex Squash bug, Anasa triszis Sycamore lace bug, Corythuca ciliata Apple leafhopper, Empoasca muligna Green rice leafhopper, Nephotertix cincliceps Oriental green rice leafhopper, Nephotettix impiciticeps Brown planthopper, Niaparvata lugen's Smaller brown planthopper, Laodelphax striatellus White backed planthopper, Sogatella furcijera Apple grain aphid, Rhopalosiphum prunifoliae Apple aphid, A phis pomi Green peach aphid, M yzus persicae Cotton aphid, Aphis gossypii Soy bean aphid, Aphis glycinae Citrus mealybug, Pseudacoccus citri Pea Weevil, Bruchus pisorum Azuki bean weevil, Callosobruchus chinensis Mexican bean beetle, Epilachna varivestis Common cabbage worm, Pierz's rapae Diamond-back moth, Plutella maculipenis Tobacco cutworm, Prodenia litura Common armyworm, Leucanea separata Mosquitoes: Aedes aegypti, Anopheles quadrimaculatus; Culex pipiens Mites: Tetranychus kanzawai, T. ulticae, Pananychus citri, P. ulmi For the purpose of demonstrating the superior properties of the present compositions to the known ones, the following experiments are carried out.

In the following tests, the compounds (1), (2) and (3) correspond to 3,4-dimethylphenyl N-methyl N-chloroacetyl carbamate, 3,5-dimethylphenyl N-methyl N-chloro-. acetyl carbamate and 3 methyl 5 isopropylphenyl N- methyl N-chloroacetyl carbamate, respectively. In the instant specification and claims, percent values are by weight unless otherwise indicated.

Test 1 Comparative test between the present compounds and substituted phenyl N-methyl carbamate derivatives in their toxicity to homothermal animals.

TEST 2 Comparative tests between the present compounds and substituted phenyl N-methyl-N-acetyl carbamates in their insecticidal activity.

(1) Acaricidal activity against the Kanzawa spider-mite (Tetranychus Kanzawai) An aqueous suspension containing the test compound was sprayed over potted seedling of kidney bean which were preliminarily infested by the Kanzawa spider-mites.

Two days after the spray, the survivial rates of the mites on the leaves were examined. The result is as follows.

TABLE 2-(1) o tth m iini sfi TEST 3 the sprayed Test compounds 5 Comparative tests between the present compounds and (1) '1 0 substituted phenyl N-methyl N-acetyl carbamate deriva- M 0 tives in their residual insecticidal activity. 0.1 0

0 (1) The residual insecticidal activity to white backed 3,4-dlmethyl phenyl N-methyl N-acetyl 1O planthopper (Sogata furcifera) and green rice leafhopcerbamate (control) 0.1 11

per (Nephotettzx apzcalzs cmclzceps) 3-methyl5isopropylphenyl N-methyl N- m3 acetylcarbammmomml) An aqeous suspension containing the test compound (untrmtedL l was sprayed over paddy rice plants (in the growth stage Increased equivalent to about 10 tillers) cultivated in 1/5,000-are (2) Insecticidal activity against the azuki bean weevil w POL Th paddy rice plants were placed in a (Callosobruchus chmens's) greenhouse and after 1, 2 and 3 days, respectively, their An acetone solution of the test compound was pipet stems were cut into about 10 cm. length, which were then onlto a Petri-dilsh (19 cm. iianlgeterzl. 'Ihfet 11 1 t the placed in glass tubes, 2 cm. in inside diameter and 15 cm. so ution was in per s irec y a er e ace one was completely evaporated, the adult females of weevil long Test j were released mto those glass tubes were introduced into the dish and then the dish was and the mortality rates at 24 hours after release were covered. A series of different dosages was tested for each 25 investigated. The result is as follows: compound and the mortality was counted 24 hours after the introduction of the insects. From the dosage-mortality TABLE 3-(1) Mortality at 24 hours after releasing Concentration (percent): Test. insects are reol the test leased oncomps. in the aqueous sus- 1 day after Zdeys alter 3 days after pension (perthe spraythee reythes re Test insects Test compounds cent) lng p ing p in; Whitebecked plenthopner (1) 0.025 100 100 75 0.05 100 100 100 Do 3,4-dlmethylphenyl N-methyl N-ecetyl carbamete (control.....; 0 0 1% t3 3 Do 3,5-dlmethylphenyl N -methyl N-acetyl cerbemete (control)...-: 0.025 10 0 0 0.05 15 0 Do 3-methyl-5-isopropylphenyl N-methyl N-ecetyl carbamate (con- 0.025 35 10 0 trol). 0.05 70 0 Do Water (control) 0 0 0 0 Green rice leafpp (1) 0.025 100 100 90 0.05 100 100 100 Do (2) 7 0.025 100 100 as 0.05 100 100 100 Do 3,4-dlmethylphenyl N-methylN-acetyl cerbemate (control)..--.' 0 0? g g 8 Do 3,5-dlmethylphenyl N-methyl N-ecetyl carbamete (control)...-.- 0.025 25 0 0 0.05 45 15 0 Do 3-meth l-5-lso rep 1 hen lN-meth lN-ece lcarbemate (con- 0.025 45 10 0 trol). p y p y y w 0.05 100 35 0 Do Water (contr l 0 0 3 0 relationship, a median lethal dose (LD-SO) was counted as seen in following table.

3-methyl-5-lsopropylphenyl N-methyl N-acetyl cerbamate (control) (2) The residual insecticidal activity to soy bean aphid (Aphis glycines) An aqueous suspension containing the test compound 31 was sprayed over potted seedlings of soy bean. Thus treated seedlings of soy bean were then placed in open air. After 1, 2 and 3 days, soy bean aphids were released on the leaves of the sprayed plants. The mortality of the 7 aphids was observed 24 hours after release.

The result is as follows.

TABLE 3(2) Mortality at 24 hours after releasing (percent): Test insects are Concentration released on of the test comps. in the w 1 day 7 2 days 3 days aqueous suspenafter the after the after the Test compounds sion (percent) spraying spraying spraying 3,4'dimethylphenyl N-methyl N-acetyl earbamate (control) 0 .025 17 0 0 0.05 67 25 0 3,5-dimethylphenyl N-methyl N acetyl carbamete (control) 0.05 33 1 1 -23 3-methyl-5-isopropylphenyl N-methyl N acetyl carbemate (control) 0 .05 67 35 Control (untreated 0 1 --13 10 1 1 Increased.

TEST 4 (2) Insecticidal activity to small brown planthopper Comparative tests between the present compound and (Delphacodes smatella) the other chloroacetyl carbamates in their residual in- O 0 On On seam d a1 actmm Int s lut1 s c taming each of the test compounds in V the following table were dipped stems of rice plant for 5 (7) The residual insecticidal actlvity t0 WhlIC-baCk0d econds respectively,

Planthopper (Sogata f '7 f and Small brown After air-drying, each stem was put in a glass tube, and plamhoPPer (Delphacodes smatella) then test insects (10 adults) were released in each glass The test was carried out in the same manner as T t tube. 2.5, 6 and 20 hours later, the rate of killed insects 3-(1) to obtain the following result. was observed to calculate mortality rate.

TABLE 4-(1) Concentration Mortality at 24 hours after reoi the test leasing (percent): Test; insects comps. in the are-released ouaqueous suspension 1 day after 2 days after Test insects Test compounds (percent) the spraying the spraying White-backed lanthopper..- (l)- 0.05 100 p 0.025 36.7 6.7

Do 2-isopropylphenyl N -methy1 N-chloroacetyl carbamate (control)-- o06022 Dn Water (nrmtrnll 0 0 Small brown lantho r-.--. 1 0.05 90.0 16.7 p ppe 0.025 0 0 p D 3 1 0.05 i 100 90.1 n 0.025 100 66.7

Do 2-isopropylphenyl N-methyl N-chloroacetyl carbamate (control)- o0&55 6.; 3

Do... Water (control) I I L i 0 0 9 The test was carried out at 28 C. The result is as follows:

carbamate is produced as oil boiling at 155 -l58 C./l. mm. Hg. Yield 88%.

TABLE 4-(2) Concentration of the test Mortality rate (percent) comps. in the aqueous 2 5 hours 6 hours 20 hours suspension after after after Test compounds (percent) releasing releasing releasing 2,4dimethylphenyl N-methyl N- ehloroacetyl carbamate (control)-.. 0 .01 30 .0 80 .0 90 .0 0 .005 0 10 .0 43 .3 o .0025 o 0 o 3-methyl-4-isopropylphenyl N- methyl N-chloroacetyl carbamate (control) 0 .01 0 0 0 0 .005 0 0 0 0 .0025 0 0 0 (3) Insecticidal activity against the azuki bean weevil (Callosobruchus chinensis) The test was carried out in the same manner as Test 2(2).

In the following examples, the relation between weight part and volume part corresponds to that between gram and milliliter.

Example Part A-Preparations of the present compounds (1) To 9.0 weight parts of 3,4-dimethylphenyl N-methyl carbamate is added 19.0 weight parts of chloroacetyl chloride, followed by heating under reflux for 4 hours.

The unreacted chloroacetyl chloride is distilled 01f under reduced pressure and 10 volume parts of water is added to the resulting residue to obtain solid substances. The solid substances are dried and then recrystallized from n-hexane to give 3,4-dimethylphenyl N-methyl N- chloroacetyl carbamate as needles melting at 56 C.-58 C. Yield 9.8 g. (77% (2) A similar procedure to the above example is taken by using 3,5-dimethylphenyl N-methyl carbamate in place of 3,4-dimethylphenyl N-methyl carbamate, whereby 3,5- dimethylphenyl N-methyl N-chloroacetyl carbamate is produced as needles melting at 73 74 C.

(3) A similar procedure to the above Example 1 is taken by using 3-methyl-5-isopropyl N-methyl carbamate in place of 3,4 dimethylphenyl N methyl carbamate, whereby 3-methyl-5-isopropyl N-methyl N-chloroacetyl Example Part B-The insecticidal composition 1) An emulsion comprising a mixture of 30 weight parts of compound (1), 50 weight parts of xylene and 20 weight parts of polyoxyethylenediphenyl ether.

(2) A wettable powder comprising a finely divided mixture of 50 weight parts of compound (2), 5 weight parts of sodium lignin sulfonate, '5 weight parts of polyoxyethylene nonylphenol ether and 40 weight parts of clay.

(3) A fine powder comprising a mixture of 2 weight parts of compound (3), and 98 weight parts of clay.

(4) A granular preparation obtained by mixing and molding 5 weight parts of compound (3), 20 weight parts of bentonite and weight parts of clay.

What is claimed is:

1. A compound having the general formula CHO r OOCHsCl UNITED STATES PATENTS 3,402,246 9/1968 Haubein 260-479 2,992,966 7/1961 Jacobi et a1. 260-479 3,167,472 1/ 1965 Czyzewski et al 260-479 3,404,208 10/ 1968 Robertson et al 260-479 JAMES A. PATTEN, Primary Examiner U.S. Cl. X.R. 

